In　recent　years,　organophotocatalytic　polymerizations　have　received　significant　interest　as　they　enable　metal-free　and　highly　efficient　macromolecular　syntheses.　Herein,　we　disclose　the　development　of　N-arylacridinium　salts　as　an　effective　class　of　photocatalysts　that　could　mediate　the　cationic　reversible　addition-fragmentation　chain　transfer　(RAFT)　polymerization　of　vinyl　ethers　with　visible　light　regulation.　Owing　to　their　high　stability　and　matched　redox　potentials　with　trithiocarbonate　chain　transfer　agents,　N-arylacridinium　salts　are　capable　of　achieving　excellent　temporal　control　over　this　cationic　RAFT　polymerization　at　room　temperature　under　the　regulation　of　blue　and　green　light.